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Well, approach them and be friendly to the guys and try to pick up the girls. If they are actually romantically together they will make this clear to you, at which point you will know what the situation is exactly. If they're bf/gf then you should eject but if it's the guy interested in the girl where there is no actual situation you can play the shit out and with very minimal effort make the other guy look like a jealous AFC and with some additional effort take the prize.
Don't ask directly because then you will be way too explicit with your intentions. Just implicitly declare them (kino, subtle references, you know.. the stuff) and see what happens.
Also to the best of my knowledge, boyfriend/girlfriend situations rarely travel to the clubs together. I barely ever encounter such a situation and if I do they're almost invariably tourists.
Thanks, Cointoss - in both cases the guy was actually friendly to me too sooo... I was having trouble getting a sense of the relationship. I've had couples talk to me just to be friendly before. But you are right, prob not a lot of couples out at clubs together. I should of escalated a little bit with the girl who got touchy-feely. The guy witnessed it and was still being friendly to me so I doubt they were together.